Potassium fluoride or a mixture of potassium fluoride and N-neopentyl-4-(dialkylamino)-pyridinium chlorides 7, 8, or 9 were used as catalysts to improve poly(ether ketone) syntheses of dichloroaryl monomers such as 1,4-bis(4-chlorobenzoyl)benzene (1) via nucleophilic displacement. Polymers of increased molecular weight within a significantly reduced reaction time can be obtained by this method, as demonstrated with condensations of 2,2-bis(4-hydroxyphenyl)pentane (4) or 2,2-bis(4-hydroxyphenyl)heptane (5) with 1. Furthermore, high molecular weight semicrystalline poly(ether ether ketone)s, commonly known as PEEKK, were synthesized by fluoride anion assisted polycondensation of 1. Under severe conditions, fluoride induced nucleophilic cleavage of the activated ether linkages of the polymers was found.